Water soluble organic ammonium per halides

ABSTRACT

Water soluble biocidal water treatment perhalides of the formula: ##STR1## where R 1  and R 2  are independently hydrogen, hydroxyethyl, alkyl, cyclic alkyl, (alpha, omega)-alkyl, alkyl ether, polyether, heterocyclic ring-substituted alkyl, and halogenated alkyl; X is chlorine, bromine or iodine; and only one of R 1  and R 2  may be hydrogen.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to novel, organic ammonium perhalides which are stable, water soluble and possess high concentrations of easily available oxidizing bromine. More particularly, this invention relates to stable, water soluble organic ammonium perhalides which have utility as water sterilization agents.

2. Description of the Art

Generally, materials which deliver oxidizable bromine have rather low water solubility, as exemplified by elemental bromine, bromine chloride and N-halogenated organics. On the other hand, materials which are water soluble, such as alkali metal bromides, require another powerful oxidizing reagent to effect the release of oxidizable bromine.

The prior art has disclosed compounds of the following Structure I: ##STR2## where R₁ -R₄ are various organic substituents, no more than one of R₁₋₄ being hydrogen, and X is chlorine, bromine or iodine.

Structure I, where R₁ -R₄ are all hydrogen, is ammonium perhalide: NH₄ XBr₂. D. H. O. John [in "Bromine and its Compounds," edited Z. E. Jolles, Part II, Chapter 1, page 114, Academic Press, New York, 1966]states that NH₄ Br₃ can be obtained by the electrolysis of a concentrated solution of ammonium bromide. A more direct method of obtaining NH₄ Br₃, mentioned by John, is to dissolve bromine in ammonium bromide solution. The prior art does not show any use or application for this compound.

Structure I where R₄ is hydrogen, R₁ R₂ R₃ NHXBr₂, also known as trisubstituted amine hydrotrihalides, is disclosed by Mercier, et al., [Proceedings of the National Academy of Science, U.S., Volume 42 pages 65 to 67 (1956)], who reported that quaternary and ternary alkylammonium chlorides and bromides dissolve readily in bromine with formation of low melting complexes. The authors gave melting points for the following perhalides:

Bu₄ NBr.Br₂ (m 76°), Bu₄ NBr.₃ Br₂ (m 37°), Me₃ NHCl.Br₂ (m 37°), Me₃ NHCl.2Br₂ (m 11.5°), Me₃ NHCl.4Br₂ (m 11.5°), Me₃ NHBr.Br₂ (m 34°), Me₃ NHBr.2Br₂ (m 6°), Me₃ NHBr.3Br₂ (m 1.5°) AM₃ NHCl.Br₂ (m 33°)

Also, C. Romers and E. W. M. Keulemans [Proceedings of the Koninklijke Nederlandse Akademie, Volume B61, pages 345-346, 1958]cited (CH₃)₃ NHBr₃ as one of the compounds formed when bromine is added to the CCl₄ solution of trimethylamine. The mechanism of its formation is not given, however.

Finally, Structure I, where none of the substituents are hydrogen, R₁ R₂ R₃ R₄ NBrX, yields tetrasubstituted ammonium perhalides. Tetraalkylammonium perhalides are well known to the prior art. Two references detail the preparation of this class of compounds: (1) Frederick D. Chattaway and George Hoyle, Journal of Chemical Society, Volume 123, pages 655 to 662, 1923; and (2) Alexander I. Popov and Robert E. Buckles, Inorganic Synthesis, Volume V, pages 176 to 178, McGraw-Hill Book Company, Inc. New York, 1957.

Morton, U.S. Pat. No. 3,152,073 describes the use of tetramethylammonium chlorodibromide for sterilizing water. Morton goes on to disclose a wide variety of tetraalkylammonium polyhalides which contain alkyl groups of six or fewer carbons, suggesting that they may be used as single reagents, directly added to water, to achieve sterilization. It has now been found that, in fact, many of Morton's compounds are not sufficiently soluble in water for use by the method disclosed.

Gannon, et al., U.S. patent application Ser. No. 048,902, filed Apr. 20, 1987, now abandoned, discloses water sterilization compositions and methods using tetrasubstituted ammonium perhalides as well as trisubstituted amine hydrotribromides. The utility of these compositons and methods has been inhibited by the poor water solubility of the compounds.

Accordingly, a primary objective of this invention is to overcome the disadvantages of the prior art materials.

A further object is to provide a composition and method of synthesis for novel organosubstituted water-soluble perbromides.

Another is to provide compositions of the character described having utility as biocidal additives in aqueous systems.

SUMMARY OF THE INVENTION

The foregoing and other objects, advantages and features of the present invention may be achieved with water soluble mono- and di-substituted ammonium perhalide compounds of the formula: ##STR3## where R₁ and R₂ are independently hydrogen or organic substituents, with only one of R₁ and R₂ being hydrogen; and R₃ and R₄ are hydrogen; and n is 2 to 6. More particularly, the compounds of the present invention include compounds of the following general formulae: R₁ R₂ NH₂ XBr_(n) and R₁ NH₃ XBr_(n), where R₁ and R₂ are independently hydrogen, hydroxyethyl, alkyl, cyclic alkyl, (alpha, omega)-alkyl, alkyl ether, polyether, heterocyclic ring-substituted alkyl, and halogenated alkyl; X is chlorine, bromine or iodine; n is 2 to 6; and only one of R₁ and R₂ can be hydrogen. These mono- and disubstituted ammonium perhalides possess high concentrations of oxidizable bromine, are stable, have good water solubility and can be easily prepared.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The water soluble mono- and di-substituted ammonium perhalides of this invention are compounds of of the following structure: ##STR4## where R₁ and R₂ are independently hydrogen, hydroxyethyl, alkyl, cyclic alkyl, (alpha, omega)-alkyl, alkyl ether, polyether, heterocyclic ring-substituted alkyl, and halogenated alkyl; X is chlorine, bromine or iodine; n is 2 to 6; and only one of R₁ and R₂ may be hydrogen. These perhalide compounds may be prepared by reacting the corresponding mono- or di-substituted ammonium hydrohalide salt with bromine.

The solubility and bromine content of the compounds depend on the bulk and nature of the substituents. The most preferred substituents are R₁ =hydroxyethyl, C₁ to C₈ alkyl groups, and R₂ =hydrogen, hydroxyethyl, or C₁ to C₈ alkyl groups.

In general, the compounds of this invention include mono- and di-substituted perhalides where X may be chlorine or iodine. It is preferred, however, to employ compounds where X is bromine, that is perbromides of the formula R₁ R₂ NH₂ --Br₃.

Specific stable, water soluble perhalides useful with the method of the present invention include ethanolammonium perbromide, propylammonium perbromide, diethanolammonium perbromide, butylammonium perbromide, methylethanolammonium per bromide, ethylethanolammonium perbromide, hexylammonium perbromide octylammonium perbromide, dipropylammonium perbromide, dibutylammonium perbromide, diethylammonium perbromide, 1,6-hexanediammonium perbromide, as well as the corresponding chloro and iodo-dibromides.

If desired, the shelf life of aqueous solutions of the compounds of this invention may be stabilized by increasing the amount of ammonium hydrohalide in relation to bromine. More particularly, up to four moles of mono- or di-substituted ammonium hydrohalide salt may be admixed with one mole of bromine. Perhalides with lower apparent vapor pressure and lower oxidizable bromine content are produced when two moles of salt in aqueous solution are added to one mole of elemental bromine. Mono- and di-substitued ammonium hydrohalide salts which may be used include those of the formula: ##STR5## where R₁ and R₂ are independently hydrogen, hydroxyethyl, alkyl, cyclic alkyl, (alpha, omega)-alkyl, alkyl ether, polyether, heterocyclic ring-substituted alkyl, and halogenated alkyl; X is chlorine, bromine, or iodine; and only one of R₁ and R₂ may be hydrogen.

Shelf life stability may also be increased by replacing part of the substituted ammonium hydrohalide salt with other stability enhancing salts such as alkali metal and ammonium bromides, especially ammonium bromide and sodium bromide, preferably in a molar ratio of about 1:1.

Preferably, the substituted ammonium hydrohalide salt and other stability enhancing salt, if any, are provided in a ratio lying in the range of about 1 to 4 moles of salt to 1 mole of bromine.

Further, it may be convenient to blend the compounds of this invention with water to produce a liquid mixture which can be easily handled by pumping and metering devices

PREPARATION OF THE COMPOUNDS OF THIS INVENTION

The compounds of this invention can be easily prepared by first reacting the corresponding amines with hydrogen halide (Equation 1), followed by the addition of bromine (Equation 2):

    (1) R.sub.1 R.sub.2 NH+HX→R.sub.1 R.sub.2 NH.sub.2 X

    (2) R.sub.1 R.sub.2 NH.sub.2 X+Br.sub.2 →R.sub.1 R.sub.2 NH.sub.2 XBr.sub.2

Most conveniently, an aqueous solution of lower alkyl- or dialkyl-ammonium perbromides can be prepared by reacting the readily available and inexpensive aqueous 48% hydrobromic acid with neat amine. The resulting aqueous amine hydrobromic salt is then readily converted to the perbromide by the addition of bromine. A simple one-pot procedure produces aqueous solutions of perbromides with exceedingly high bromine content.

Another method of preparing the same compound consists of first dissolving the bromine in hydrobromic acid, followed by the addition of the neat amine:

    (3) HBr+Br.sub.2 →HBr.sub.3

    (4) HBr.sub.3 +R.sub.1 R.sub.2 NH→R.sub.1 R.sub.2 NH.sub.2 XBr.sub.2

Still another method for the preparation of these compounds, especially if higher bromine content in the solution is desired, consists of reacting a more concentrated hydrobromic acid with amine, followed by bromine addition. Alternatively, the corresponding aqueous solution of the amine hydrobromide can be concentrated by evaporating water, followed by the addition of appropriate amount of bromine.

Finally, anhydrous perbromides can also be easily prepared by gently heating the dry amine hydrobromide salt with bromine.

Analogous procedures may be employed to produce the chlorine and iodine containing perhalides of this invention by employing the corresponding hydrogen halide in the foregoing reactions.

The perhalides of this invention include those containing additional bromine. The bromine content of these perhalides may be increased by adding more than one mole of bromine to the substituted-ammonium hydrobromide, yielding a higher perbrominated salt, as illustrated by Equation (5).

    (5) R.sub.1 R.sub.2 NH.sub.2 Br+2Br.sub.2 →R.sub.1 R.sub.2 NH.sub.2 Br.sub.5

Although four or more moles of bromine can be added to the aqueous amine hydrobromide, the solution, upon contact with excess water, releases elemental bromine. However, it is possible to prepare solutions of perbromides in which the bromine content approached R₁ R₂ NH₂ Br₅ and which did not release bromine upon contact with excess water.

SHELF LIFE STABILITY OF AQUEOUS PERBROMIDES

Aqueous solutions of perhalides have surprisingly good shelf life stability. Generally, in aqueous solution, monoalkylammonium perbromides are more stable than dialkylammonium perbromides. Furthermore, the more dilute the perbromide solution, the lower its stability unless stabilized with additional stabilizer additives.

In aqueous solution, the perhalides of this invention, though high in bromine content, show surprisingly low vapor pressure of bromine. Liquid elemental bromine has a vapor pressure of approximately 220 mm Hg at 26° C. and bromine water (containing approximately 3.5% by weight of bromine) shows a vapor pressure of 210 mm Hg at 26° C. These values can be compared to roughly 40-60 mm Hg measured for various perbromides containing roughly 40% oxidizable bromine. Again, for the sake of comparison, aqueous NaBr₃ containing roughly 40% Br₂ has a vapor pressure of 140 mm Hg. Of course, the vapor pressure of the aqueous perbromides of the present invention can be further reduced by the addition of ammonium or alkali metal bromide salts.

The following examples will detail the preparation, properties and stability of the preferred perbromides in accordance with the present invention.

PREPARATION OF PERBROMIDES Example 1 Compound #1: Ethanolammonium Perbromide

In a 5.0.1., four-necked round-bottom flask, immersed in an ice bath and equipped with a mechanical stirrer, reflux condenser, addition funnel, and thermometer, HBr (48%) (1940 g./11.5 moles) is placed. Ethanolamine (703 g./11.5 moles) is slowly added in at a rate such that the temperature does not exceed 50° C. to ensure minimal loss of HBr.

After the addition of the ethanolamine is completed, the reaction mixture (61.8% ethanolamine hydrobromide) is allowed to cool to room temperature. Then, bromine (1840 g./11.5 moles) is carefully added via an addition funnel, and the temperature is maintained below 5020 C. The yield of the dark red aqueous ethanolammonium perbromide is 4483 g.

The perbromide was then titrated for oxidizable bromine via the method described in "Standard Methods for the Examination of Water and Waste Water," 15th edition: Method 408A. Data for Compound #1 are given in Table 1.

Other water soluble organic ammonium perbromides identified as Compounds #2-9 in Table 1 were prepared via the procedure used for Compound #1, but on a reduced scale. Data for these compounds are also reported in Table 1.

                                      TABLE 1                                      __________________________________________________________________________     COMPLETELY SOLUBLE PERBROMIDES PREPARED FROM AQUEOUS SOLUTION                  Compound                                Calc. Ox. Br.sub.2 *                                                                  Tit. Ox.                                                                              Theo. Ox. Br.sub.2                                                             **                       #     Name              Structure       % by Weight                                                                           % by Weight                                                                           % by                     __________________________________________________________________________                                                           Weight                   1     Ethanolammonium Perbromide                                                                       HOCH.sub.2 CH.sub.2 NH.sub.3 Br.sub.3                                                          41.0   40.8   52.9                     2     Butylammonium Perbromide                                                                         CH.sub.3 (CH.sub.2).sub.3 NH.sub.3 Br.sub.3                                                    39.8   38.1   50.9                     3     Propylammonium Perbromide                                                                        CH.sub.3 (CH.sub.2).sub.2 NH.sub.3 Br.sub.3                                                    41.2   39.3   53.4                     4     Diethanolammonium Perbromide                                                                     (HOCH.sub.2 CH.sub.2).sub.2 NH.sub.2 Br.sub.3                                                  36.9   36.5   46.2                     5     Methylethanolammonium Perbromide                                                                 (CH.sub.3)(HOCH.sub.2 CH.sub.2)NH.sub.2 Br.sub.3                                               39.5   39.3   50.6                     6     Ethylethanolammonium Perbromide                                                                  (CH.sub.3 CH.sub.2)(HOCH.sub.2 CH.sub.2)NH.sub.2                               Br.sub.3        38.1   37.7   48.4                     7     Dimethylethanolammonium                                                                          (CH.sub.3).sub.2 (HOCH.sub.2 CH.sub.2)NHBr.sub.3                                               38.1   37.2   48.4                           Perbromide                                                               8     Hexylammonium Perbromide                                                                         CH.sub.3 (CH.sub.2).sub.5 NH.sub.3 Br.sub.3                                                    37.2   36.1   46.7                     9     Octylammonium Perbromide                                                                         CH.sub.3 (CH.sub.2).sub.7 NH.sub.3 Br.sub.3                                                    34.9   34.7   43.2                     __________________________________________________________________________      *Oxidizable bromine calculated on an aqueous mass balance.                     **Theoretical oxidizable bromine content of the neat compound            

A series of additional perbromides identified as Compounds #10-14 were prepared using the procedure described above. However, after the addition of the bromine was completed, two liquid phases were produced. The top phase was an aqueous layer and contained a minimal amount of bromine. The bottom phase, a viscous liquid, represented the perbromide, which in most instances contained oxidizable bromine very close to the theoretical oxidizable bromine content of the neat compound. Data for Compounds 10-14 are given in Table 2.

                                      TABLE 2                                      __________________________________________________________________________     PARTIALLY SOLUBLE PERBROMIDES PREPARED FROM AQUEOUS SOLUTION                   Compound                            Tit. Ox. Br                                                                             Theo. Ox. Br**                                                                          Solubility               #     Name         Structure        % by Weight.sup.2                                                                       % by Weight.sup.2                                                                       (g./100 g H.sub.2        __________________________________________________________________________                                                           O)                       10    Dipropylammonium                                                                            (CH.sub.3 (CH.sub.2).sub.2).sub.2 NH.sub.2 Br.sub.3                                             45.1     46.7     10                             Perbromide                                                               11    Dibutylammonium                                                                             (CH.sub.3 (CH.sub.2).sub.3).sub.2 NH.sub.2 Br.sub.3                                             40.9     43.3     1.0                            Perbromide                                                               12    Tributylammonium                                                                            (CH.sub.3 (CH.sub.2).sub.3).sub.3 NHBr.sub.3                                                    36.0     37.5     0.01                           Perbromide                                                               13    Triethylammonium                                                                            (CH.sub.3 CH.sub.2).sub.3 NHBr.sub.3                                                            45.6     46.7     0.1                            Perbromide                                                               14    Diethylethanolammonium                                                                      (CH.sub.3 CH.sub.2).sub.2 (HOCH.sub.2 CH.sub.2)NHBr.sub                        .3               42.3     44.7     0.1                      __________________________________________________________________________      **Theoretical oxidizable bromine content of the neat compound.           

Compounds #15 and #16 were prepared using the foregoing procedure. The perbromides produced were crystalline solids which precipitated as the bromine addition proceeded. Data for Compounds 15 and 16 are shown in Table 3.

                                      TABLE 3                                      __________________________________________________________________________     PERBROMIDES WHICH PRECIPITATED OUT OF AQUEOUS SOLUTION                         Compound                     Tit. Ox. Br                                                                            Theo. Ox. Br**                                                                          Solubility                       #     Name        Structure  % by Weight.sup.2                                                                      % by Weight.sup.2                                                                       (g./100 g                        __________________________________________________________________________                                                   H.sub.2 O)                       15    Diethylammonium                                                                            (CH.sub.3 CH.sub.2).sub.2 NH.sub.2 Br.sub.3                                               47.9    50.9     15                                     Perbromide                                                               16    1,6-Hexanediammonium                                                                       Br.sub.3 H.sub.3 N(CH.sub.2).sub.6 NH.sub.3 Br.sub.3                                      51.8    53.5     50                               __________________________________________________________________________      **Theoretical oxidizable bromine content of the neat compound.           

Compounds #7, #12, #13, #14, which are all trisubstituted amine hydroperbromides, were prepared for comparison purposes. All except Compound #7 are only sparingly soluble in water and thus are unsuitable for use where high water solubility is required. The water solubility of the perbromides which separated from the solution are shown in Tables 2 and 3. Again, with the exception of Compound #7, they are all significantly more soluble than the tri-substituted ammonium hydortribromides.

Example 2 Concentrated Organic Ammonium Perbromides

By concentrating the salt solution used, aqueous perbromides may be obtained with higher oxidizable bromine concentrations; These concentrated salt solutions may be prepared in two different ways: (1) the aqueous salt solution may be evaporated to the desired concentration; or (2) a more concentrated HBr may be used. The procedure for preparing a perbromide, using HBr (62%), is described below and the compound is listed as Compound #17 in Table 4.

Compound #17: Concentrated Aqueous Ethanolammonium Perbromide

Using the setup described in the preparation of Compound #1, HBr (62%) (500 g./3.8 moles) was placed in a round-bottom flask. Ethanolamine (234 g./3.8 moles) was slowly dripped into the flask. After the neutralization was complete, yielding a 74.1% salt solution, bromine (612 g./3.8 moles) was carefully dripped into the reaction flask.

                                      TABLE 4                                      __________________________________________________________________________     CONCENTRATED AND ANHYDROUS ORGANIC AMMONIUM PERBROMIDES                        Compound              Concentration of                                                                        Tit. Ox. Br                                                                            Calc. Ox. Br                            #     Name            Hydrobromide %                                                                          % by Weight.sup.2                                                                      % by Weight .sup.2                                                                     M.P. (°C.)               __________________________________________________________________________     17    Ethanolammonium Perbromide                                                                     74.1     47.3    45.5    Liquid                          18    Ethanolammonium Perbromide                                                                     100      51.8    52.9    47-53                           19    Propylammonium Perbromide                                                                      100      53.2    53.4    25-29                           20    Diethanolammonium Perbromide                                                                   100      45.3    46.2    35-45                           __________________________________________________________________________

Anhydrous Organic Perbromide.

By using a completely anhydrous amine hydrobromide salt, it was possible to produce solid organic ammonium perbromides. Compound #18, shown in Table 4, is described below.

Compound #18: Solid Anhydrous Ethanolammonium Perbromide

Ethanolammonium bromide (10 g./0.07-moles), prepared by the neutralization of HBr (48%) by ethanolamine and evaporated to dryness, was placed in a beaker. Bromine 11.2 g./0.07 moles) was added, and the beaker was covered with parafilm. The beaker was carefully heated to 35° C., at which point the contents of the beaker became a homogenous liquid. The beaker was allowed to sit overnight at room temperature (24° C.). By morning, the perbromide had crystallized.

Two other solid perbromides, solid propylammonium perbromide (Compound #19) and solid diethanolammonium perbromide (Compound #20), were very soluble in water and were prepared in the same manner (see Table 4).

Example 3

Perbromides with lower apparent vapor pressure and lower oxidizable bromine content are produced when two moles of the hydrobromide are salt are added to one mole of elemental bromine. If the second mole of salt is the same corresponding amine hydrobromide, then the perbromides are exemplified by Compounds #21-23. The procedure for preparing a 2:1 (salt:bromine) aqueous ethnolammonium perbromide (Compound #21) is described below. However, if the second salt is different, as exemplified by Compounds #24 and #25, then the desired second saltr can be added either as a solid or an aqueous solution, followed by the additon of bromine. The procedure for preparing Compound #24 is shown below. Data for Compounds #21-25 are given in Table 5.

                                      TABLE 5                                      __________________________________________________________________________     STABILIZED AQUEOUS ORGANIC AMMONIUM PERBOMIDES                                 Compound                         Tit. Ox. Br                                                                            Calc. Ox. Br                          #     Name            Stab. Salt Used                                                                           % by Weight.sup.2                                                                      % by Weight .sup.2                    __________________________________________________________________________     21    Ethanolammonium Perbromide                                                                     HOCH.sub.2 CH.sub.2 NH.sub.3 Br                                                           25.4    25.8                                  22    Propylammonium Perbromide                                                                      CH.sub.3 (CH.sub.2).sub.2 NH.sub.3 Br                                                     26.9    28.6                                  23    Diethanolammonium Perbromide                                                                   (HOCH.sub.2 CH.sub.2).sub.2 NH.sub.2 Br                                                   20.5    22.6                                  24    Ethanolammonium Perbromide                                                                     NaBr       24.4    24.8                                  25    Ethanolammonium Perbromide                                                                     NH.sub.4 Br                                                                               23.6    24.8                                  __________________________________________________________________________

Compound #21: Aqueous 2:1 (Salt:Bromine) Ethanolammonium Perbromide

The ethanolamine hydrobromide salt is prepared via the neutralization of HBr (48%) with ethanolamine as described by Compound #1. Ethanoloamine hydrobromide (459.2 g./2.0 moles) is placed in a 500 ml round-bottom flask, equipped with a mechanical stirrer, thermometer, and addition funnel. Bromine (159.8 g/1 mole) is slowly added. A dark red liquid (612 g./98.9% yield based on mass balance) with very low visible vapor pressure is obtained.

Compound #24: Aqueous Ethanolammonium Perbromide Stabilized with NaBr

NaBr (26 g./0.25 moles) is dissolved in water (38 g.). The resulting solution is added to the ethanolammonium perbromide solution (100 g., containing 0.25 moles ethanolammonium hydrobromide and 0.25 moles of bromine). The perbromide produced has a very low vapor pressure.

Example 4 Higher Perbromides

Further addition of bromine to the aqueous organic ammonium perbromides is possible. These perbromides have a higher available oxidation bromine content and are still soluble in water. Data for these perbromides are listed in Table 6. The calculated n of HOCH₂ CH₂ NH₃ BrBr_(n) molecule is also shown. Compound #29, which had an added bromine concentration of approximately 51%, is the only perbromide that formed pools when a one-ml sample was placed in 200 ml of water.

                  TABLE 6                                                          ______________________________________                                         HIGHER AQUEOUS                                                                 ETHANOLAMMONIUM PERBROMIDE                                                                       Tit.     Calc.                                               Com-  Grams Br.sub.2                                                                             Ox. Br.sub.2                                                                            Ox. Br.sub.2                                        pound Added to    % by     % by       H.sub.2 O                                #     100 g Cpd #1                                                                               Weight   Weight n1/ Solubility                               ______________________________________                                         26    24.6        52.6     52.5   3.2 Completely                               27    46.9        57.7     59.7   4.3 Completely                               28    69.0        63.9     65.0   5.5 Completely                               29    106.0       72.6     71.3   7.3 Formed pools                             ______________________________________                                          1/n calculated for formula HOCH.sub.2 CH.sub. 2 NH.sub.3 BrBr.sub.7      

Perbromide Shelf Life Stability Studies

In order to determine the shelf life stability of the perbromide solutions, a series of studies were conducted to determine the percent bromine lost over time. The following tables shown below list the perbromides studied and the percent oxidizable bromine lost over time. The perbromides studied were kept in closed bottles in ambient conditions (Table 7) and at 50° C. (Table 8).

                                      TABLE 7                                      __________________________________________________________________________     PERBROMIDE CLOSED-BOTTLE STABILITY AT AMBIENT TEMPERATURE                      Compound              Initial Ox. Br.sub.2                                                                   Final Ox. Br.sub.2                                                                              Relative                                                                                Time Elapsed           #     Name of Perbromide                                                                             % by Weight                                                                            % by Weight                                                                            Change in % Br.sub.2                                                                    in % Br.sub.2                                                                           (months)               __________________________________________________________________________     1     Ethanolammonium 40.1    38.5    1.6      4.0      24                     3     Prophylammonium 41.3    41.0    0.3      0.7      17                     4     Diethylammonium 37.0    35.0    2.0      5.4      24                     11    Dibutylammonium 43.2    41.1    2.1      4.9      16                     21    Stabilized Ethanolammonium                                                                     25.4    24.9    0.5      2.0      24                     22    Stabilized Propylammonium                                                                      25.6    25.0    0.6      2.3      24                     23    Stabilized Diethanolammonium                                                                   22.1    19.7    2.4      10.9     22                     30    Diluted Compound #1                                                                            20.0    18.0    1.0      5.0      24                     31    Diluted Compound #3                                                                            20.0    18.2    1.8      9.0      24                     32    Diluted Compound #4                                                                            20.0    16.6    3.4      17.0     24                     __________________________________________________________________________

                                      TABLE 8                                      __________________________________________________________________________     PERBROMIDES CLOSED-BOTTLE STABILITY AT 50° C.                           Compound              Initial Ox. Br.sub.2                                                                   Final Ox. Br.sub.2                                                                              Relative                                                                                Time Elapsed           #     Name of Perbromide                                                                             % by Weight                                                                            % by Weight                                                                            Change in % Br.sub.2                                                                    in % Br.sub.2                                                                           (months)               __________________________________________________________________________     1     Ethanolammonium 40.8    39.0    1.8      4.4      40                     3     Prophylammonium 41.0    39.0    2.0      4.9      40                     4     Diethylammonium 37.0    30.0    7.0      18.9     40                     21    Stabilized Ethanolammonium                                                                     25.8    25.0    0.8      3.1      40                     22    Stabilized Propylammonium                                                                      25.6    24.9    0.7      2.7      40                     23    Stabilized Diethanolammounium                                                                  22.5    16.6    5.9      26.2     40                     30    Diluted Compound #1                                                                            20.0    17.2    2.8      14.0     40                     31    Diluted Compound #2                                                                            20.0    17.0    3.0      15.0     40                     32    Diluted Compound #3                                                                            20.0    10.6    9.4      47.0     40                     __________________________________________________________________________

Vapor Pressure of Perbromides

The vapor pressures of the aqueous organic ammonium perbromides were measured using an isoteniscope as described by Farrington, et al. [Farrington, D.; Alberti, R.; William, S.; Corwell, C.; Bender, P; and Harriman, S. Experimental Physical Chemistry, Experiment 17, pp. 164-165, 7th Edition, McGraw Hill Publishing Co., New York, 1976]. Data are reported in Table 9.

                  TABLE 9                                                          ______________________________________                                         VAPOR PRESSURE MEASUREMENTS OF                                                 ORGANIC AMMONIUM PERBROMIDES                                                   Com-   Ox. Br.sub.2      % by      Vp (mmHg                                    pound #                                                                               Name of Perbromide                                                                               Weight    @ 26° C.)                            ______________________________________                                          1     Ethanolammonium   40.8      52                                           3     Propylammonium    39.3      36                                           4     Diethylammonium   36.5      49                                           5     Methylethanolammonium                                                                            39.3      28                                           7     Dimethylethanolammonium                                                                          37.2      30                                          11     Dibutylammonium   43.3      38                                          12     Tributylammonium  37.5      28                                          17     Conc. Ethanolammonium                                                                            47.3      57                                                 (62% HBr)                                                               21     Stabilized        25.4      36                                                 Ethanolammonium                                                         27     Bromine-loaded    57.7      116                                                Ethanol-ammonium                                                        33     Sodium (NaBr.sub.3)                                                                              37.9      145                                         34     Bromine in H.sub.2 O                                                                             3.5       210                                         35     Pure Bromine      100       223                                         ______________________________________                                    

The water soluble perhalides of this invention can be easily and economically prepared. They are surprisingly stable and have a high concentration of oxidizable bromine. This class of compounds is useful in all water treatment and other applications where stability and high bromine are desirable. 

I claim:
 1. Water soluble ammonium perhalides of the formula: ##STR6## where R₁ and R₂ are independently hydrogen, hydroxyethyl, alkyl, cycloalkyl, alkyl ether, polyoxyalkylene, and halogenated alkyl; X is chlorine, bromine or iodine; n is 2 to 6; and only one of R₁ and R₂ may be hydrogen.
 2. Water soluble perhalides, as claimed in claim 1, wherein X is bromine.
 3. Water soluble perhalides, as claimed in claim 2, wherein R₁ is a member selected from the group consisting of hydroxyethyl and C₁₋₈ alkyl and R₂ is a member selected from the group consisting of hydrogen, hydroxyethyl and C₁₋₈ alkyl.
 4. Ethanolammonium perbromide, HOCH₂ CH₂ NH₃ 13 Br₃.
 5. Propylammonium perbromide, CH₃ CH₂ CH₂ NH₃ --Br₃.
 6. Diethanolammonium perbromide, (HOCH₂ CH₂)₂ NH₂ --Br₃. 